Method of preparing polyfluorinated sulphonic acid and derivatives

ABSTRACT

NEW PRODUCTS AND COMPOSITIONS OF MATTER COMPLYING WITH THE GENERAL FORMULA:   (CNF2N+1$CH2$BSO2-Z)DM   WHEREIN: CNF2N+1 REPRESENTS A STRAIGHT OR RAMIFIED BRANCHED PERFLUORINATED CHAIN: N REPRESENTS A WHOLE NUMBER BETWEEN 1 AND 20, B IS A WHOLE NUMBER BETWEEN 2 AND 20, PREFERABLY EQUAL TO 2 OR 4, Z REPRESENTS A CHLORINE, BROMINE OR AN OXYGEN ATOM (WHEN Z IS A CHLORINE OR A BROMINE ATOM, M IS NOTHING AND D IS EQUAL TO 1), WHEN Z IS AN OXYGEN ATOM: M IS A HYDROGEN ATOM IN WHICH CASE, D IS EQUAL TO 1, M IS A METAL OF THE GROUPS IA, IIA, IB, IIB, VIII OF THE PERIODIC TABLE, THE AMMONIUM RADICAL, THE ALUMINUM OR THE LEAD RADICAL, AND IN WHICH CASE D REPRESENTS THE VALENCE OF THIS METAL AND METHODS FOR PREPARING NEW PRODUCTS AS ILLUSTRATED BY THE FOLLOWING REPRESENTATIVE REACTIONS.

Int. Cl. c07r 7/24 US. Cl. 260-435 R Claims ABSTRACT OF THE DISCLOSURENew products and compositions of matter complying with the generalformula:

wherein: C F J represents a straight or ramified branched perfiuorinatedchain: It represents a whole number between 1 and 20, b is a wholenumber between 2 and 20, preferably equal to 2 or 4, Z represents achlorine, bromine or an oxygen atom (when Z is a chlorine or a bromineatom, M is nothing and d is equal to 1), when Z is an oxygen atom: M isa hydrogen atom in which case, d is equalto 1, M is a metal of theGroups I II I I1 VIII of the periodic table, the ammonium radical, thealuminum or the lead radical, and in which case d represents the valenceof this metal and methods for preparing new products as illustrated bythe following representative reactions.

This application is a division of our application Ser. No. 851,081,filed Aug. 18, 1969.

SUMMARY OF THE INVENTION The present invention involves new industrialcompounds or products complying with the general formula:

wherein: C F represents a straight or ramified branched perfiuorinatedchain; n represents a number between 1 and 20, b is a whole numberbetween 2 and 20, preferably equal to 2 or 4, Z represents a chlorine,bromine or an oxygen atom (when Z is a chlorine or a bromine atom, M isnothing and d is equal to 1), when Z is an oxygen atom; M is a hydrogenatom and in which case, d is equal to 1 or M is a metal of the GroupsI,,, II 1 H VIII of the periodic table, the ammonium radical, thealuminum or the lead radical and in which case d represents the valenceof this metal. The novel compounds are prepared as illustrated by thefollowing representative reactions:

wherein Y=Nr or I.

(3) C F {-CH 9 ,SO Cl+2Na0H- C F2 1'(CH2')1;SO3Na. H20 wherein n and bare as represented above.

DESCRIPTION OF THE PREFERRED EMBODIMENT The preparation ofpolyfluorinated sulphocyanides C F tCH ,SCN used in reaction 1) has beendescribed in the French Pat No. 1,861,360 of the applicant.

3,825,577 Patented July 23, 1974 The oxidation of, a polyfiuorinatedsulphocyanide having the formula C F tCH -),,SCN by the chlorine or thebromine is easily carried out when the sulphocyanide is dissolved in asuitable solvent as a reaction medium. It is preferred to use as asolvent a water-acetic acid mixture containing between 5 and 25% of thewater by volume.

A reaction temperature between about 15 C. and 120 C., can generally beused but it is preferred to use a reaction temperature between 15 C. andC.

During the reaction (1) a by-product is obtained, namely thepolyfluoroalkane halide, whose formula is C F -CH X wherein X is thechlorine or the bromine. The polyfluorinated sulphocyanide can beregenerated by reaction with an alkaline sulphocyanide according to thereaction:

The action of a mineral sulphite on a polyfluoroalkane halide C F tcH hY(Y being the iodine or the bromine) as shown in equation (2) above iscarried out under the classicial conditions of the Streckers reaction.The reaction can be carried out in the presence of many solvents such aswater, an alcohol (preferably ethanol), a ketone (preferably acetone),or an aprotic solvent (preferably dimethylformamide ordimethylsulphoxide). A mixture of solvents falling in the above classescan be used. It is preferred however, to use a mixture of water andethanol, volume per volume.

The applicants have also discovered that the addition of a smallquantity of copper turnings aids in the nucleophile attack of thepolyfluoroalkane halide by the sulphite ion.

The reaction can be carried out at a temperature between about 20 and250 C., preferably between 50 and 150. If the reaction temperature isabove the boiling point of the reaction mixture or one of itsconstituents, it can be carried out in an autoclave (see Example 9).

The polyfluorinated sulphonates as set forth in equation (3) above, mayalso be obtained by neutralizing the halides of polyfluorinatedsulphonic acids C F {-CH ,SO Z with the aid of a base of the formula M(0H),, where M and d have the meanings designated above. Thisneutralizing is carried out under the usual conditions for this kind ofreaction. The reaction can be carried out in the presence of manysolvents, such as water, an ether (such as isopropyl ether), a ketone(such as acetone) or their mixtures. It is preferred, however, tooperate in the presence of water. The reaction temperature can bebetween about 10 and C. but preferably at about 20 C. An increase in thereaction temperature, although it is not necessary, may accelerate thereaction owing to the solubility.

The new compounds of this invention are useful in the textile industry,and in the leather and paper industries. They can also be employed ascorrosion inhibitory agents.

surface active agents and levelling agents. The compounds can thus beincorporated in waxes, greases, varnishes and starting fiuorinatedmaterial.

EXAMPLE 1 Chlorine was bubbled to 20, for 3 h. at the rate of 4 l./h.,through a mixture of C F -C H SCN (20.5 g.; 0.1 mole), icy acetic acid(100 cm?) and water (12 cm. at 20 C. for 3 hours at the rate of 4l./hour. After 1 hour and 45 minutes, the temperature rose to 61 C. in15 minutes. It remained at this value for 15 minutes and then itgradually went down to the ambient temperature. The chlorine output wasthen stopped and the apparatus surged with a nitrogen flow for 30minutes. A solid (4.1 g.) was then filtered from the reaction mixturethe main constituent of which was ammonium chloride. The filtrate wasdistilled and 4 fractions and one residue was obtained as follows:

(a) Fraction 54-60/100 mm., 58.1 g. was composed of water and aceticacid (b) Fraction 625/ 100 mm. Water (100 cm?) was added to thisfraction, and a dense phase was decanted (7.6 g.) composed of water(2.6%), acetic acid (11.6%) and C F -C H SO Cl (85.8%; 29.6 mmole) (c)Fraction 6292/ 100 mm.; 4.8 g. was composed of C F C H -Cl(l%), aceticacid (70%) and C2F5C2H4-SO2C1 mmole) (d) Fraction 927/100 mm.; 6.5 g.was composed of C F C H Cl (2.8% C F -C H 4O Cl (92.4%; 24.7 mmole) andthree unindentified compounds (4.8%

(e) Solid residue, 3.2 g. unidentified solid,

C F --C H -SO Cl was obtained with a conversion rate of 66.5%.

EXAMPLE 2 Chlorine, at the rate of 4 l./hour, was bubbled at 50 C. for 3hours and 30 minutes through a mixture of (30.5 g.; 0.1 mole), icyacetic acid (100 cm. and water (12 cm. After 30 minutes, the temperaturerose to 75 C. and remained at this value for 30 minutes before graduallygoing down to the ambient temperature. After stopping the chlorineoutput, the apparatus was purged with a nitrogen flow for 30 minutes. Asolid (3.9 g.) was then filtered from the mixture, the main constituentof which was ammonium chloride. The filtrate was distilled, twofractions and one residue were obtained:

(2.) Fraction 50-64/100 mm., constituted of water and acetic acid (b)Fraction 90-95/20 mm.; 27.4 g. composed of C F C H -Cl (3.4% C F -C H-SCN (12.3% 10 mmole) and C F C H SO Cl (84.3%; 23.6 mmole) (c) Solidresidue 4.6 g. unidentified solid C F C H SO Cl was obtained with aconversion rate of 68% and a yield of 75.5%.

EXAMPLE 3 Chlorine, at the rate of 5 l./hour, was bubbled for 2 hoursthrough a mixture of C F C H SCN (40.5 g.; 0.1 mole), icy acetic acid(100 cm?) and water 12 cmfi). The reaction vessel was maintained at 63C. The introduction of the chlorine caused a rise in the temperature to72 C. after 30 minutes. This temperature remained stable for 30 minutes,then gradually went down to 63 C. The chlorine output was stopped andthe apparatus purged with a nitrogen flow for 30 minutes. A mineralsolid (4.9 g.) was removed from the mixture by filtering, the main I I II component was ammonium chloride. The filtrate was distilled and 4fractions and one residue were obtained as follows:

(a) 5260/ 100 mm.; composed of water and acetic acid (b) 626/l00 mm.; 61g. 50 cm. of water was added to this fraction, and a dense phase 1.5 g.)decanted composed of C F C H SO CI (68%; 2.4 mmole) and C F C H Cl (32%)Monochloroacetic acid (9.2% acetic acid (31%) (d) 108-11S/20 mm.; 33.4g.; C F C H .SO Cl (85.4%; 65 mmole), C F C H Cl (14.6%; 11 mmole) (e)Residue 1.5 g. unidentified.

C F C H SO Cl was obtained with a conversion rate of 70% and a yield of78.5%.

EXAMPLE 4 Chlorine, at the rate of 4 l./hour, Was bubbled for 4 hoursthrough a mixture of C F -C H fi8CN (50.5 g.; 0.1 mole), icy acetic acid(100 cm. and water (12 cm. The reaction vessel was maintained at 50 C.15 minutes after introducing chlorine, the temperature rose to 62 C.This temperature remained stable for 1 hour, and gradually went down to50 C. The chlorine output was then stopped and the apparatus purged witha nitrogen bow for 30 minutes. A solid (52.8 g.) was filtered from thereaction mixture and recrystallized in 90 cm. of carbon tetrachloride. Amineral solid (4 g.) was removed by filtration in a hot state and thefiltrate cooled down to 20 C., and a solid A (37.2 g.) filteredtherefrom. The last filtrate was concentrated to 20 cmfi, which resultedin the precipitation of a solid B (7.4 g.) which was filtered therefrom.The solids A and B are identical and comply with the formulaC3F17C2H4SOZCL C F C H SO Cl was obtained with a conversion rate of81.5%.

EXAMPLE 5 Chlorine at the rate of 4 l./hour, was bubbled at 75 C. for 2hours through a mixture of (30.3 g.; 0.05 mole), water (6 cm?) and icyacetic acid (50 cmfi). After 30 minutes, the temperature rose to C., andit remained at this value for 45 minutes and then gradually went down to75 C. After stopping the chlorine output, the apparatus was purged witha nitrogen flow for 30 minutes. A solid (34 g.) was filtered from thereaction mixture and recrystallized in 200 cm. of carbon tetrachloride.The solid was collected (29.3 g.) which was composed of C F C H -SO Clmmole) and of C F -C H SO Cl was obtained with a conversion rate of 76%and a yield of EXAMPLE 6 A mixture of C2F5C2H4'I H1016), Na SO (25 g.;0.2 mole), water (50 cmfi), ethanol (50 cmfi) and a turning of copper (1g.) was maintained at a temperature of 78 C. for 48 hours. The reactionmixture formed was a liquid and a solid. A solid A (26 g.) was obtainedtherefrom by filtration and washed with 25 cm. of water. A solid B (17g.) remained. The filtrate was distilled and two fractions and oneresidue were obtained as follows:

(a) 49/200 mm.; ethanol (b) 60/200 mm.; water (0) residue This residuewas washed with 10 cm. of water and separated by filtering a solid C (6g.). The solids B and C were collected and recrystallized in awater-ethanol mixture (50 cm. per 100 cm?) 20.1 g. of.

vrivere-collected which corresponds to a conversion rate of which afterdrying at 120 C. weighed 17.2 g.

The filtrate was distilled and three fractions were obtained as follows:

(a) Fraction 60/400 mm. This fraction was composed of two phases, theywere stirred with 50 cm. of water and the two phases collected, bydecanting, the densest phase (16.2 g.) was composed of C F C H --I (98%;0.041 mole and ethanol (2%).

(b) Fraction 65/400 mm.: ethanol (c) Fraction 80 /400 mm.: water and fewethanol.

C F,C H -SO Na was thus recovered with a conversion rate of 49% and ayield of 83% EXAMPLE 8 A mixture of C F C H I (47.4 g.; 0.1 mole), Na sQl (25 g.; 0.2 mole), water (50 cm?) and ethanol (50 emi was maintainedat 78 C. for 48 hours in a suitable reaction vessel. The reactionmixture resulting was a liquid and a solid. The solid was filteredtherefrom and washed with 100 cm. of water, and after filtering, thesolid was dried in a drying vessel at 120 C., 20 g. of C F C H -SO Nawere thus obtained.

The filtrate was distilled and one fraction and one residue wereobtained as follows:

(a) Fraction 49/200 mm.: ethanol (b) Residue. This residue containedwater and a solid. The solid (0.9 g.) was filtered and was the sulfonateC F C H --SO Na. The filtrate was evaporated and a solid (4.1 g.) whoseorigin is mainly mineral was obtained.

C F C H -SO Na was thus obtained with a conversion rate of 46.5%.

EXAMPLE 9 A mixture of C F C H I (47.4 g.; 0.1 mole), Na SO (25 g.; 0.2mole), water (50 cm. ethanol (50 cm?) and a turning of copper (1 g.) wasmaintained at 120 C. for 48 hours in an autoclave. The maximum pressurewas 3 hrs. After cooling down the autoclave to 20 C., the reactionmixture was composed of a liquid and a solid. The solid was filtered andweighed 53 g. The solid was washed with 100 cm. of water and afterfiltering, it was recrystallized in one liter of water. The solidcollected (35 g.) was the polyfiuorinated sulphonate C F C H SO Na; theconversion rate amounted to 78%.

EXAMPLE 10 A mixture of C F {C H I (25 g. 0.5 mole) Na SO (12.5 g.; 0.1mole), water (25 cmfi), ethanol (25 cm?) EXAMPLE 11 M p v 20 crn. ofNaOH (10 N) were rapidly added to C F 'C H -SO Cl (10.93 g.; 0.02 mole).During this addition, the temperature rose from 20 to 45C. The mixturewas then brought to and maintained at 100 C. for 4 hours. A solid wasrecovered therefrom by filtering. This solid was washed with water (3X20 emf), dried and collected. The solid (10.9 g.) was thepolyfiuorinated sulphonate C3F17C H SO3Na The conversion rate amountedto 99%.

EXAMPLE 12 A mixture of C F C H -SO Cl (11.16 g.; 0.025 mole), water (40cm. and sulphuric acid at 66 C. B (12 g.) was maintained at 100 C. for 8hours. The mixture was then extracted with ethyl ether (4X 50 cm. andthe ether eliminated or removed by distillation. The resulting residualsolid was dried under vacuum. The dry solid obtained (8.8 g.) was thesulphonic acid melting between 73 and 79 C. The conversion rate was82.5%.

EXAMPLE 13 Chlorine at the rate of 14 l./ho11r was passed for 4 hoursthrough a mixture of C F (CH CH SCN (108.5 g.; 0.25 mole), glacialacetic acid (200 cm. and water (27 cm. brought to a temperature of 52 C.The reaction being exothermic, the temperature rose from 52 C. to 72 C.in 30 minutes, then gradually went down to 55 C. The reaction mixturewas then washed with water (twice 100 cm. at a temperature of 50 C. Thusa dense phase was recovered by decantation, which became solid bycooling down to 20 C. The solid thus obtained was finely crushed andwashed with water (100 cm?) at 20 C. The solid was filtered, then driedunder vacuum. This solid (114.8 g.) was composed of C F (CH CH 'SO Clwith a purity of 92%.

EXAMPLE 14 Chlorine at the rate of 12 l./hour was passed for 3 hoursthrough a mixture of C F (CH CH SCN (53.4 g.; 0.1 mole), glacial aceticacid (100 cm?) and water (12 cm. brought to a temperature of 67 C. Thereaction being exothermic the temperature rose from 67 C. to 75 C. in 30minutes, then gradually went down to 67 C. in 2 hours. The reactionmixture was then washed with water (100 cm. at 50 C. Thus a dense phasewas recovered by decantation, which became solid by cooling down to 20C. The solid thus obtained was finely crushed and washed with water (100cm?) at 20 C. The solid was filtered, then dried under vacuum. Thissolid (51 g.) was composed of c F tcH -CH i So Cl with a purity of 95%It is to be understood that the phrase glacial acetic acid designatesmore accurately than the phrase Icy acetic acid the product mentioned inthe present invention, in col. 3, line 13; col. 3, lines 46 and 68; col.4, line 23; and col. 4, line 45.

We claim:

1. The method of preparing compounds of the formula [C F {-CI-I) ,SO Mwherein M is a metal of Groups I II I H and VHI of the periodic table,an am- 7 monium'radical, aluminum or lead whichcdmpriss reacting acompound of the formula G F ficl-ifi Y, wherein Y is bromine or iodinewith"a-'nietal 'sulfite ofG'roup s I II I I1 and VIII of the per'iodict'able, ammonium sulfite, lead sulfite or aluminum sulfite' -in which nis a number between 1 and 20, b is a number-betWeetT' Z -and 20, and dis equal to the valence-of themetal-f'i 5:

2. The method of claiml vin vt lhich the reaction is carried out in thepresence of a solvent. 1 k u I 3. The method of claim 2 in which "thesolvent is a member of the group consisting of water, alcohol, ketones,an aprotic solvent or mixture thereof.

4. The method of claim 2 in which a small'amount of copper is added tothe reaction mixture.

5. The method of claim 1 in which the reaction temperature is betweenabout 20 and 250 C.

1,851,102 3/1932 Kaii'shem. 260-513 B 1,867,793 7/1932 1,842,626 1/19322,694,723 11/1954 2,797,239 6/1957 2,732,398 1/1956 "2,877,267 3/1959 8References Cited UNITED STATES PATENTS V- UNITED STATES PATENT OFFICECERTIFICATE OF CORRECTION Patent No. 3,825,577 Dated July 23, 1974Inventor(s) JEAN LALU and LOUIS FOULLETIER It is certified that errorappears in the above-identified patent and that said Letters Patent arehereby corrected as shown below:

Column 1, line 5 reads "Chemiques" should be --Chimiques-.

Column 1, line 58 reads "cl HzO" should be -'-c1 /H o--.

Column 1, line 72 reads "Pat No l,86l,360",should be --Patent No.'fi-,561',36o--.

Column 3, line 12 reads "4 l./h.," should be 4 l/h,--.

Signed and sealed this 21st day of January 1975.

[SEAL) Attesta MCCOY M. GIBSON JR. C. MARSHALL DANN Attesting OfficerCommissioner of Patents FORM po'wso USCOMM-DC eoa7s.| e9 I U.5.GOVERNMENT PRINTING OFFICE I969 0-366-334,

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 825,577Dated July 23, 1974 Inv ntor JEAN PIERRE LALU and LOUIS FOULLE'I'IER Itis certified that error appears in the above-identified patent and thatsaid Letters Patent are hereby corrected as shown below:

Column 1, line 5 reads "Chemiques" should be --Chimiques--.

Column 1, line 58 reads Cl H O" should be -Cl /H O--.

Column 1, line 72 reads "PatwNo l,86l,360"fsh ould be --Paten t No.l,56l',360-.

Column 3, use 12 reads "4 l./h.," should be 4 l/h,--.

Signed and sealed this 21st day of January 1975.

(SEAL) Attestz MCCOY M. GIBSON JR. 7 C. MARSHALL DANN Attesting OfficerCommissioner of Patents

